EP0049777A2 - Homogeneous liquid dyeing preparation - Google Patents

Abstract

1. A homogeneous fluid colorant for coloring glue, comprising 20 to 70% of colouring constituents consisting of one or more soluble anionic or cationic dyes, and one or more finely divided pigments ; water ; water-soluble organic solvents and dispersants ; and, if desired, water-soluble organic acids.

Description

The invention relates to liquid colorants which are characterized in that they contain one or more soluble dyes, one or more finely divided pigments and solvents and, if appropriate, dispersants.

Suitable readily soluble dyes are cationic, nonionic and anionic dyes, the ionogenic dyes generally being made readily soluble in the solvent used by means of suitable anions or cations.

Cationic dyes for the colorants according to the invention mainly come from the di- or triarylmethane, xanthene, azo, cyanine, azacyanine, methine, acridine, safranine, oxazine, indulin or nigrosine series. Individual connections are e.g. Basic Yellow 2 (CI 41000), Basic Red 1 (CI 45160), Basic Violet 10 (CI 45170), Basic Blue 26 (CI 44045), Basic Blue 7 (CI 42595), Basic Blue 1 (CI 42025), Basic Violet 1 (CI 42535), Basic Violet 3 (CI 42555), Basic Green 1 (CI 42040), Basic Green 4 (CI 42000) and phenazine dyes such as Solvent Blue 7 (CI 50400). Dyes from the azo, triarylmethane and xanthene series are preferred.

Suitable anions for aqueous colorants are those customarily derived from inorganic acids and lower carboxylic acids, such as chloride, bromide, sulfate, methosulfate, ethosulfate, nitrate, formate, acetate or propionate. If solubility in organic solvents is essential, long-chain carboxylic acid anions such as oleate are particularly suitable.

The highly solubilizing anions can also be introduced by reacting the cationic dyes in the form of the associated color bases with the acids which provide the anions.

Examples of color bases are Solvent Yellow 34 (CI 41010: 1), Solvent Orange 3 (CI 11270: 1), Solvent Red 49 (CI 45170: 1), Solvent Violet 8 (CI 42532: 1), Solvent Violet 9 (CI 42555 : 1), Solvent Blue 2 (CI 42563: 1), Solvent Blue 4 (CI 44045: 1) and Solvent Black 7 (CI 50415: 1).

Nonionic dyes for the colorants according to the invention originate predominantly from the azo, nitro or anthraquinone series, preferably the compounds listed in the color index under solvent dyes.

Suitable anionic dyes are, in particular, compounds containing sulfonic acid groups from the azo, anthraquinone, metal complex, triarylmethane or stilbene series, with azo dyes and phthalocyanine derivatives being particularly preferred.

• 2,5-Dichlor-4- → 3-Cyano-4-methyl-2,6-di(ß-hy--sulfo-anilin droxy-ethylamino)-pyridin - (als Dibutyl-ethanolaminsalz),
• 2-Hydroxy-3-nitro- → 1-Phenyl-3-methyl-pyrazolon-5 -5-sulfo-anilin (als Chrom-(1:2)-Komplex)
• 2-Hydroxy-4-sulfo-6- →β-Naphthol (als Chom-(1:2)--nitro-naphthylamin-1 -Komplex) und
• 2-Hydrox_Y-3-sulfo-5- → 1-Phenyl-3-methyl-pyrazolon-5 -nitro-anilin (als Chrom-(1:2)-Komplex).

Individual anionic dyes are, for example, the dyes Acid Yellow 3 (CI 47005), Acid Yellow 36 (CI 13065), Acid Yellow 19 (CI 18967), Acid Orange 7 (CI 15510), Acid Orange 8 (CI -1 15575), Acid ^{Red 88} ( ^{CI 15620} ) _, Acid ^Red 351 (CI 28683), Acid Violet 90 (CI 18762), Acid Blue 9 (CI 42090), Acid Blue 193 (CI 15707), Direct Blue 86 (CI 74180) such as

• 2,5-dichloro-4- → 3-cyano-4-methyl-2,6-di (ß-hy - sulfo-aniline hydroxyethylamino) pyridine - (as dibutylethanolamine salt),
• 2-hydroxy-3-nitro- → 1-phenyl-3-methyl-pyrazolon-5 -5-sulfo-aniline (as chromium (1: 2) complex)
• 2-hydroxy-4-sulfo-6- → β-naphthol (as chromium (1: 2) - nitro-naphthylamine-1 complex) and
• 2-Hydrox _Y -3-sulfo-5- → 1-phenyl-3-methyl-pyrazolon-5-nitro-aniline (as a chromium (1: 2) complex).

As water-solubilizing cations alkali (Li⊕, Na⊕, K⊕), ammonium and substituted ammonium cations, in particular alkanolammonium cations are to be mentioned in particular.

Colorants according to the invention for organic solvents are particularly suitable as anionic dyes, metal complex dyes, e.g. the chromium or cobalt complexes of azo or azomethine dyes and copper phthalocyanine dyes.

Longer-containing alkylammonium residues are particularly suitable as cations for the dyes; corresponding dyes are e.g. in German patents 12 26 727, 12 63 947 and 23 34 228.

A prerequisite for usability in the colorants according to the invention is that all dyes mentioned can be dissolved in as high a concentration as possible. The dyes can also be used in the form of concentrated dye solutions and methods for the preparation of such solutions are described in particular in the patent literature, e.g. in patent applications P 30 20 891.4, P 30 36 556.1, DE-AS 12 40 036, DE-AS 20 49 620, DE-OS 22 28 260, DE-OS 28 52 863, DE-OS 28 16 506 or DE- AS 24 13 369 and DE-PS 1 259 484 and DE-PS 2 334 228.

Inorganic and organic pigments are suitable as pigments. The only requirement for their usability is that they can be finely distributed in the colorant. A representative selection of suitable pigments can be found in the Color Index, chapter Pigments. Individual preferred pigments and pigment groups are, for example: carbon black, iron oxides, phthalocyanines, azo pigments, nickel titanium yellow, chrome yellow, molybdate orange, milori blue and quinacridone, perylene, oxazine and anthraquinone pigments.

Inexpensive pigments such as carbon black, iron oxides, azo compounds and phthalocyanines are preferred for economic reasons.

Practically all compounds which are normally used for the production of aqueous pigment dispersions are suitable as dispersants. Both anionic and cationic, preferably nonionic, dispersants are suitable. Suitable nonionic surfactants are, for example, polyethylene glycols and ethoxylation products based on linear fatty acids, fatty amines, fatty acid amides and fatty alcohols. Suitable anionic dispersants are, for example, fatty alcohol ether-1 sulfates and alkylphenol ether sulfates. Quaternary ammonium salts of long-chain fatty alkylamines, for example, can be used as cationic surfactants. When using anionic or cationic surfactants, however, care must be taken to avoid reactions with the anionic or cationic dye.

The colorants according to the invention contain water and / or organic solvents.

The choice of the organic solvent or solvents for the colorants according to the invention depends on the intended use of these colorants. For example, flexographic inks typically contain polar solvents, but varnishes and wax solutions contain non-polar solvents.

Suitable polar organic solvents are e.g. Alkanols, glycols, glycol ethers, amides, tetrahydrofuran, butyrolactone, dioxane, dimethyl sulfoxide, lower carboxylic acid esters, ketones and aliphatic carboxylic acids, of which formic acid and acetic acid are preferred.

Long-chain aliphatic alkanols, carboxylic acids, esters, ketones or ethers and preferably aliphatic and aromatic hydrocarbons and halogen-substituted hydrocarbons are suitable as non-polar and less polar organic solvents.

The colorants according to the invention contain dyes and pigments in amounts of about 20-70%, preferably 40-60%. The quantitative ratio of soluble dye to pigment can be varied within wide limits, which are essentially determined by the desired color and economic factors. The proportion of polar (incl sive water) and / or non-polar solvents is 30-80%, preferably 40-60%, based on the total amount. The amount of acids and surfactants which may be present can be up to 30%, preferably 5 to 20%.

The selection of the dyes naturally also depends on the intended use and the solubility in the given medium.

For the preparation of the colorants according to the invention, e.g. mix the solution of a readily soluble dye in an organic solvent with a preferably non-aqueous pigment dispersion. But you can also disperse a pigment directly in the dye solution. Of course, other substances such as thickeners or binders can also be added to the colorants according to the invention. Details of the production can be found in the examples, in which information on parts and percentages, unless stated otherwise, relates in each case to the weight.

The colorants according to the invention are suitable on the one hand for dyeing aqueous media of all kinds, e.g. of paper pulps, glues, wood impregnating agents, crop protection agents, fertilizers, also for dyeing and impregnating glass fibers and glass wool, jute felt, aqueous printing inks, grid fabrics for carpet underlays etc. The water-containing colorants according to the invention are particularly valuable for dyeing glues, such as those used for the production of chipboard be used.

On the other hand, the colorants according to the invention are particularly suitable for dyeing media of all kinds containing organic solvents, for example of polishing materials, candles, printing ^r ben, lacquers, wood impregnating agents, crop protection agents, adhesives, etc. suitable. The colorants according to the invention containing organic solvents are particularly valuable for dyeing shoe polish.

The colorants according to the invention offer, in particular, economic advantages over previously used dyes. It was particularly surprising that they can be produced in a homogeneous form and stored without segregation.

example 1

2 parts of a liquid dye containing 40% C.I. Acid Orange 7 (C.I. 15510) 1 part of a pigment preparation containing 35% carbon black (C.I. Pigment Black 7) as well as nonionic dispersant and glycol are mixed with stirring. The result is a liquid, slightly thixotropic colorant mixture with good shelf life.

Example 2

1 part of a liquid dye containing 45% C.I. Basic Violet 49 (preparation is described in DE-OS 22 28 260 / Example 3) and 1 part of a pigment preparation containing 40% iron oxide red (C.I. Pigment Red 101) as well as nonionic dispersants and glycol are mixed with stirring. A well flowing mixture is obtained which can be easily incorporated into aqueous media.

Example ₃

2 parts of a liquid dye containing 45% C.I. Basic Violet 49 (see Ex. 2) and 1 part of a pigment preparation containing 60% iron oxide red (C.I. Pigment Red 101) as well as non-ionic dispersing agents and dipropylene glycol are mixed with stirring. A well flowing dough is obtained which is readily miscible with aqueous media.

Example 4

2 parts of a liquid dye containing 45% C.I. Basic Violet 49 (see Example 2) and 1 part of a pigment preparation containing 35% carbon black (C.I. Pigment Black 7) as well as nonionic dispersant and glycol are mixed with stirring. The result is a liquid colorant mixture with good flowability and storage stability.

Example 5

2 parts of a liquid dye containing 40% C.I. Acid Orange 7 (see Example 1) and 1 part of a pigment preparation containing 40% copper phthalocyanine blue (C.I. Pigment Blue 15: 1) and nonionic dispersant and glycol are mixed with stirring. The storage-stable mixture obtained can be easily stirred into aqueous media.

Example 6

200 parts of a liquid dye containing 40% C.I. Acid Orange 7 (see Example 1), 45 parts of a transparent iron oxide red (C.I. Pigment Red 101), 5 parts of an oxyethylated fatty alcohol, 20 parts of ethylene glycol and 80 parts of water are ground on a stirred ball mill for one hour. The dough-shaped colorant obtained is stable in storage, free of specks and easily miscible with aqueous media.

Example 7

100 parts of a liquid dye containing 45% C.I. Basic Violet 49 (see Example 2), 120 parts of iron oxide red (C.I. Pigment Red 101), 5 parts of an oxyethylated fatty alcohol, 20 parts of ethylene glycol and 40 parts of water are ground on an agitator ball mill for one hour. A well-flowing dough is obtained which can be easily incorporated into aqueous media.

Example 8

100 parts of a liquid dye containing 45% CI Basic Violet 49 (see Example 2), 80 parts of β-copper phthalocyanine blue (CI Pigment Blue 15: 3), 5 parts of an ethoxylated fatty alcohol, 20 parts of ethylene glycol and 80 parts of water are ground on an agitator ball mill for one hour. The dough-shaped mixture obtained is readily flowable and perfectly miscible with aqueous media.

Example 9

₁₀ 0 parts of an orange-colored liquid dye (see Example 3, DE-OS 28 52 919), 80 parts of β-copper phthalocyanine blue (CI Pigment Blue 15: 3), 5 parts of an oxyethylated fatty alcohol, 20 parts of ethylene glycol and 40 parts of water are mixed on one Agitator ball mill grated for one hour. A well flowing dough is obtained which can be easily stirred into aqueous media.

Example 10

₂ 00 parts of a liquid dye containing 40% CI Acid Orange 7 (see Example 1), 250 parts of iron oxide red (CI Pigment Red 101), 10 parts of a condensation product of β-naphthalenesulfonic acid and formaldehyde (as sodium salt), 20 parts of ethylene glycol and 20 parts Water is driven on an agitator ball mill for one hour. The storage-stable dough obtained is well suited for coloring aqueous media.

Example 11 '

100 parts of a liquid dye containing 45% C.I. Basic Violet 49 (see Example 2), 120 parts of iron oxide red (C.I. Pigment Red 101), 5 parts of C12 / C14-fatty alkyl-dimethyl-benzyl-ammonium chloride, 20 parts of ethylene glycol and 3 parts of polyvinylpyrrolidone are ground on a stirred ball mill for one hour. A storage-stable, free-flowing dough is obtained which is very well tolerated with aqueous media.

Example 12

10 parts of pigment C.I. Pigment Blue 15: 3, C.I. 74160, (ß-copper phthalocyanine blue) are rubbed with 90 parts of a solution of a brown oxazine dye (70% in 2-ethylhexanol) on a stirred ball mill for one hour.

The Braun dye was prepared by oxidation of 2-ethylhexyl-o-phenylenediamine and is described in application P 30 20 891.4, example 4.

A black, free-flowing concentrate is obtained which is suitable for dyeing shoe polish.

Example 13

20 parts of a pigment paste based on CI Pigment Blue 15: 3 and 80 parts of the solution of a brown oxazine dye (corresponding to Example 12) are mixed with stirring. This gives a free-flowing, black mixture which is stable in storage and can be easily incorporated into wax mixtures containing gasoline. 1

The pigment paste above contains' 25% C.I. Pigment Blue 15: 3 (ß-copper phthalocyanine), 15% dispersant and 60% of a solvent mixture consisting of 7 parts of a high-boiling aromatic hydrocarbon mixture and 3 parts of ethyl glycol acetate.

Example 14

25 parts of a pigment paste from C.I. Pigment Blue 15: 1, C.I. 74160 (α-copper phthalocyanine blue) in a short oil alkyd resin are mixed with stirring with 75 parts of the solution of a brown oxazine dye (corresponding to Example 12).

The result is a liquid colorant mixture with good flowability and storage stability, which e.g. is well suited for black shoe polish.

Example 15

10 parts of the pigment CI Pigment Violet 27, CI 42535: 3, (colored paint of methyl violet) are rubbed with 90 parts of the solution of a brown oxazine dye (corresponding to Example ₁₂ ) on a stirred ball mill for 1 hour.

The good flowing colorant is stable in storage, free of specks and easily miscible with systems based on organic solvents.

'Example 16

20 parts of the pigment C.I. Pigment Blue 27 (Milori blue) are rubbed with 80 parts of the solution of a brown oxazine dye (corresponding to Example 12) on a stirred ball mill for 1 hour.

A well flowing black mixture is obtained, which e.g. suitable for coloring shoe polish.

Example 17

15 parts of the pigment CI Pigment Yellow 12, CI 21090 (Benzidine Yellow) are mixed with 85 parts of the solution of the condensation product of _1,4-D i-hydroxyanthraquinone and 2,3-dihydro-1,4-diaminoanthraquinone with ß-Ethylhexoxypropylamin, ß -Ethylhexylamine and γ-methoxypropylamine are ground on a stirred ball mill for 1 hour.

A thin, dark green colorant preparation is obtained which is miscible with organic solvents.

Example 18

20 parts of the pigment C.I. Pigment Yellow 42, C.I. 77492, (iron oxide yellow) are rubbed with 80 parts of a liquid dye concentrate for 30 minutes on a stirred ball mill. The liquid dye concentrate consists of the 50% solution of the azo dye from o-aminoazotoluene → β-phenylethyl-naphthol-2 (mixture of isomers, described in DE-OS 28 52 863) in a mixture of aromatic hydrocarbons.

The resulting thin, red colorant mixture is stable in storage, does not tend to flocculate or settle and is suitable for dyeing media based on organic solvents.

Example 19

30 parts of a pigment paste based on C.I. Pigment Blue 15: 3 (corresponding to Example 13) are mixed with 40 parts of a color base digestion of 40% C.I. Solvent Blue 4, C.I. 44045, (Victoria blue base B) mixed in 60% olein and 30 parts toluene with stirring.

A low-viscosity color paste with good storage stability is obtained, which can be used for coloring all kinds of organic media, such as wax solutions, printing inks and lacquers.

Example 20

10 parts of the pigment C.I. Pigment Blue 15: 3 (β-copper phthalocyanine blue) are rubbed with 88 parts of the solution of a brown oxazine dye (corresponding to Example 12) and 2 parts of a vinylpyrrolidone / vinyl acetate copolymer on a stirred ball mill for 1 hour.

The colorant preparation obtained is suitable for dyeing alcoholic flexographic printing inks. The prints made with it have a perfect sublimation fastness. This preparation can also be used for document-compatible ballpoint pen pastes, for example according to the following recipe: 100 parts of the black mixture mentioned 25 parts of benzyl alcohol 25 parts phenylglycol 10 parts oleic 5 parts 1,2-propylene glycol 35 parts phthalate resin

The writing obtained with this ballpoint pen paste cannot be removed by water, ethanol, acetone or toluene.

Example 21

• 34 % des 1:2-Kobalt-Mischkomplexes aus 4-Nitro-2-aminophenol -1-Phenyl-3-methylpyrazolon und 4-Nitro-2-aminophenol → β-Naphthol,
• 33 % Dimethylformamid und
• 33 % Butyldiglykol.

20 parts of a pigment paste based on CI Pigment Blue 15: 3 (corresponding to Example 13) are mixed with 80 parts of a liquid dye of the following composition:

• 34% of the 1: 2 cobalt mixed complex of 4-nitro-2-aminophenol -1-phenyl-3-methylpyrazolone and 4-nitro-2-aminophenol → β-naphthol,
• 33% dimethylformamide and
• 33% butyl diglycol.

A low-viscosity colorant preparation is obtained which has good storage stability, does not tend to flake and is suitable for dyeing all types of media based on organic solvents.

Example 22

12 parts of a pigment paste based on CI Pigment Blue 15: 3 (corresponding to Example 13) are mixed with 88 parts of the 60% solution of an orange dye in a high-boiling aromatic hydrocarbon solvent with stirring. The preparation of the orange dye is described in DE-AS 24 34 110 / Example 1.

The low-viscosity, brown colorant obtained can be obtained by adding suitable thickeners, e.g. colloidal silica can be stabilized. It is suitable e.g. for coloring shoe polish.

Example 23

50 parts of a yellow liquid dye (a) are mixed with 50 parts of a pigment paste (b) based on copper phthalocyanine blue with stirring. 5 parts of this free-flowing mixture are stirred into 95 parts of flexographic varnish (c). The green flexographic printing ink obtained in this way is easy to print and has good waterfastness.

The yellow liquid dye (a) mentioned is C.I. Basic Yellow 2 (C.I. 41,000) in the form of dodecylbenzenesulfonate, dissolved approx. 65% in a mixture of ethyl glycol and methyl isopropyl ketone.

The pigment paste (b) contains approx. 30% C.I. Pigment Blue 15: 2, C.I. 74 160, dispersed in a mixture of dodecylbenzenesulfonic acid, rosin and toluene.

The flexographic varnish (c) contains 10% styrene / maleic acid copolymer _" 8% synthetic varnish 82% ethanol / ethyl glycol (mixture 9: 1).

Example 24

33 parts of a yellow liquid dye (a) 'and 67 parts of a pigment preparation (b) based on copper phthalocyanine blue are mixed with one another with stirring. 5 parts of this mixture are stirred into 95 parts of an aqueous binder solution (c). A strong, green flexographic printing ink is obtained which is suitable for printing on paper, for example for cement sacks.

The yellow liquid dye (a) mentioned is the azo dye from flavonic acid (= 4,4'-diamino-stilbene-2,2-disulfonic acid), diazotized and coupled to phenol, as an approx. 25% solution in one Mixture of neopentyl glycol and water.

The pigment preparation (b) contains approx. 40% C.I. Pigment Blue 15: 1, dispersed in a mixture of nonionic dispersants, glycol and water.

The binder solution (c) contains as saponifiable resin 25% of an ester of phthalic acid and trimethylolpropane, saponified with ammonia and dissolved in a mixture of n-propanol and water.

Claims (7)

1. Liquid colorants containing one or more soluble dyes, one or more finely divided pigments and solvents and, if appropriate, dispersants. 2. Colorants according to claim 1, characterized in that they contain anionic or cationic dyes as soluble dyes and water and / or water-soluble solvents and optionally organic acids as solvents. 3. Colorants according to claim 1, characterized in that they contain readily soluble dyes as soluble dyes in organic solvents and organic solvents as solvents. 4. Colorants according to claim 1 and 2, characterized in that they contain anionic azo dyes or phthalocyanine derivatives as soluble dyes. 5. Colorants according to claim 1 and 2, characterized in that they contain cationic dyes of the azo, triarylmethane or xanthene series as soluble dyes. 6. Colorants according to claim 1 and 3, characterized in that they contain non-ionic compounds from the series of solvent dyes as soluble dyes or cationic or anionic dyes solubilized in organic solvents by corresponding anions or cations. 7. Colorants according to claims 1 and 2, characterized in that they contain carbon black, iron oxides, azo compounds or phthalocyanines as pigments.